Effect of biomass-derived synthesis gas impurity elements on cobalt Fischer–Tropsch catalyst performance including in situ sulphur and nitrogen addition

Borg, Øyvind; Hammer, Nina; Enger, Bjørn Christian; Myrstad, Rune; Lindvåg, O.A.; Eri, Sigrid; Skagseth, Torild Hulsund; Rytter, Erling

doi:10.1016/j.jcat.2011.01.015

Cited by 117 publications

(82 citation statements)

References 28 publications

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“…For example, the CO conversion dropped from 38% to 10% within 100 h of co-feeding 500 ppmv of KNO 3 and stabilized, even with further potassium nitrate addition (500 ppmv). This phenomenon was also observed in recent studies (Khodakov, Chu et al 2007;Borg, Hammer et al 2011).…”

Section: Impact Of Kno 3 and Kcl On Co-ft Catalystsupporting

confidence: 88%

“…The methane (9.0 wt.%) and C 5+ (80 wt.%) selectivity also remained relatively unchanged with NH 4 NO 3 addition, as shown in Figure 44. It should be noted that Claeys et al reported that co-feeding up to 25% NH 3 in the syngas did not significantly affect the FischerTropsch synthesis activity over a cobalt catalyst, and Borg et al observed no change in activity when ammonia was added at concentrations up to 4.2 ppmv during cobalt-catalyzed FT synthesis (Claeys, van Steen et al 2010;Borg, Hammer et al 2011). At the end of our 400 h test, the catalyst did appear to slowly recover from exposure to the contaminant under clean baseline feed conditions.…”

Section: Impact Of Ash 3 On Co-ft Catalystmentioning

confidence: 99%

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Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

Alptekin

2013

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Co-gasification of biomass and coal in large-scale, Integrated Gasification Combined Cycle (IGCC) plants increases the efficiency and reduces the environmental impact of making synthesis gas ("syngas") that can be used in Coal-Biomass-to-Liquids (CBTL) processes for producing transportation fuels. However, the water-gas shift (WGS) and Fischer-Tropsch synthesis (FTS) catalysts used in these processes may be poisoned by multiple contaminants found in coal-biomass derived syngas; sulfur species, trace toxic metals, halides, nitrogen species, the vapors of alkali metals and their salts (e.g., KCl and NaCl), ammonia, and phosphorous. Thus, it is essential to develop a fundamental understanding of poisoning/inhibition mechanisms before investing in the development of any costly mitigation technologies.We therefore investigated the impact of potential contaminants (H 2 S, NH 3 , HCN, AsH 3 , PH 3 , HCl, NaCl, KCl, AS 3 , NH 4 NO 3 , NH 4 OH, KNO 3 , HBr, HF, and HNO 3 ) on the performance and lifetime of commercially available and generic (prepared in-house) WGS and FT catalysts; ferrochrome-based high-temperature WGS catalyst (HT-WGS, Shiftmax 120™, Süd-Chemie), low-temperature Cu/ZnO-based WGS catalyst (LT-WGS, Shiftmax 230™, Süd-Chemie), and iron-and cobalt-based Fischer-Trospch synthesis catalysts (Fe-FT & Co-FT, UK-CAER). In this project, TDA Research, Inc. collaborated with a team at the University of Kentucky Center for Applied Energy Research (UK-CAER) led by Dr. Burt Davis.We first conducted a detailed thermodynamic analysis. The three primary mechanisms whereby the contaminants may deactivate the catalyst are condensation, deposition, and reaction. AsH 3 , PH 3 , H 2 S, HCl, NH 3 and HCN were found to have a major impact on the Fe-FT catalyst by producing reaction products, while NaCl, KCl and PH 3 produce trace amounts of deposition products.The impact of the contaminants on the activity, selectivity, and deactivation rates (lifetime) of the catalysts was determined in bench-scale tests. Most of the contaminants appeared to adsorb onto (or react with) the HT-and LT-WGS catalysts were they were co-fed with the syngas:  4.5 ppmv AsH 3 or 1 ppmv PH 3 in the syngas impacted the selectivity and CO conversion of both catalysts  H 2 S slowly degraded both WGS catalysts -A binary mixture of H 2 S (60 ppmv) and NH 3 (38 ppmv) impacted the activity of the LT-WGS catalyst, but not the HT-WGS catalyst  Moderate levels of NH 3 (100 ppmv) or HCN (10 ppmv) had no impact  NaCl or KCl had essentially no effect on the HT-WGS catalyst, but the activity of the LT-WGS catalyst decreased very slowly Long-term experiments on the Co-FT catalyst at 260 and 270 °C showed that all of the contaminants impacted it to some extent with the exception of NaCl and HF. Irrespective of its source (e.g., NH 3 , KNO 3 , or HNO 3 ), ammonia suppressed the activity of the Co-FT catalyst to a moderate degree. There was essentially no impact the Fe-FT catalyst when up to 100 ppmw halide compounds (NaCl and KCl), or up to 40 ppmw alkali ...

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Section: Impact Of Kno 3 and Kcl On Co-ft Catalystsupporting

confidence: 88%

Section: Impact Of Ash 3 On Co-ft Catalystmentioning

confidence: 99%

Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

Alptekin

2013

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“…In a study on the effect of impurities it was found [37], by impregnating 400 ppm of the impurity element from nitrate precursors, a poisoning effect which decreases in the following order: Na > Ca > K > Mg > P, Mn, Fe and Cl showing minimal effects. The latter is surprising as chlorine causes a 25% reduction in hydrogen chemisorption.…”

Section: Causes Of Deactivationmentioning

confidence: 99%

Deactivation and Regeneration of Commercial Type Fischer-Tropsch Co-Catalysts—A Mini-Review

2015

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Deactivation of commercially relevant cobalt catalysts for Low Temperature Fischer-Tropsch (LTFT) synthesis is discussed with a focus on the two main long-term deactivation mechanisms proposed: Carbon deposits covering the catalytic surface and re-oxidation of the cobalt metal. There is a great variety in commercial, demonstration or pilot LTFT operations in terms of reactor systems employed, catalyst formulations and process conditions. Lack of sufficient data makes it difficult to correlate the deactivation mechanism with the actual process and catalyst design. It is well known that long term catalyst deactivation is sensitive to the conditions the actual catalyst experiences in the reactor. Therefore, great care should be taken during start-up, shutdown and upsets to monitor and control process variables such as reactant concentrations, pressure and temperature which greatly affect deactivation mechanism and rate. Nevertheless, evidence so far shows that carbon deposition is the main long-term deactivation mechanism for most LTFT operations. It is intriguing that some reports indicate a low deactivation rate for multi-channel micro-reactors. In situ rejuvenation and regeneration of Co catalysts are economically necessary for extending their life to several years. The review covers information from open sources, but with a particular focus on patent literature.

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“…Issues explored using SSITKA have included among others the study of mechanisms, the presence and implications of site heterogeneity, the role of chemical promoters and the effect of operation conditions on the surface coverage of intermediates. For FTS, the use of SSITKA has resulted in an improved understanding on the effect of catalyst properties (promoters [72][73][74][75][76][77][78][79][80][81][82][83], support [84][85][86][87][88][89][90], particle size etc. [91][92][93][94]) and the reaction conditions [95][96][97][98][99][100][101] on the performance.…”

Section: Approaches Of Kinetic Analysis For Ftsmentioning

confidence: 99%

Recent Progresses in Understanding of Co-Based Fischer–Tropsch Catalysis by Means of Transient Kinetic Studies and Theoretical Analysis

Yang

Chen

et al. 2014

Catal Lett

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During the last years it has been an increasing focus on fundamental studies of the Fischer-Tropsch synthesis (FTS). Steady-state isotopic transient kinetic analysis and first principles investigation have proven to be important methods in studying the reaction mechanism of FTS. The present contribution deals with recent progresses in understanding of the F-T mechanism on Co catalysts based on combined DFT calculations, in situ characterization, steady-state isotopic transient kinetic analysis and microkinetics. A brief outlook into future perspectives of the FTS for converting synthesis gas from different carbon sources to fuels and chemicals is also provided.

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Effect of biomass-derived synthesis gas impurity elements on cobalt Fischer–Tropsch catalyst performance including in situ sulphur and nitrogen addition

Cited by 117 publications

References 28 publications

Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

Impact of Contaminants Present in Coal-Biomass Derived Synthesis Gas on Water-gas Shift and Fischer-Tropsch Synthesis Catalysts

Deactivation and Regeneration of Commercial Type Fischer-Tropsch Co-Catalysts—A Mini-Review

Recent Progresses in Understanding of Co-Based Fischer–Tropsch Catalysis by Means of Transient Kinetic Studies and Theoretical Analysis

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